A New Catalytic Route to Monoalkynyl-Functionalized Di- and Trivinyl-Substituted Cyclosiloxanes and Divinylcyclosilazanes

作者：Dudziec Beata; Marciniec Bogdan^*

来源：Organometallics, 2008, 27(21): 5598-5604.

DOI：10.1021/om800361k

Series of alkynyltrimethyldivinylcyclotrisiloxanes and -trisilazanes, and of alkynyltetramethyltrivinylcyclotetrasiloxanes have been synthesized by means of a new catalytic coupling of the appropriate tri- and tetra-vinylcyclosiloxanes (1, 2) and trivinylcyclosilazane (3) with terminal alkynes R-C=C-H (where R = SiEt(3), SiMe(2)Ph, GeEt(3), or alkyl) in the presence of a ruthenium hydride complex [RuHCl(CO)(PCy(3))(2)] (1), as a catalyst. Twenty-one new functionalized monoalkynyl-substituted cyclosiloxanes and cyclosilazanes were isolated in high to moderate (70-95%) yields and characterized by (1)H, (13)C, and (29)Si NMR spectroscopy. Selected alkynyldivinyl- and alkynyltrivinyl-cyclic products have been further functionalized by silylative coupling of the remaining vinyl groups with styrene to give cyclosiloxanes and cyclosilazanes containing one alkynyl and two or three styryl substituents at silicon in high yields and selectivity ((E)styryl products).

• 出版日期2008-11-10